878
Bull. Chem. Soc. Jpn. Vol. 86, No. 7 (2013)
Annulation of 2H-Pyran onto 1-Oxa- or 1-Azacyclohexane-2,4-diones
17.5, 4.1 Hz) (total 2H), 1.64 (d, J = 5.2 Hz, 3H); 13C NMR
(151 MHz, CDCl3): ¤ 164.6, 164.1, 161.6, 142.1, 141.9, 135.9
(two peaks), 135.5 (two peaks), 129.3 (two peaks), 126.1
(two peaks), 125.9-125.4 (multiple peaks), 125.1, 113.9 (two
peaks), 101.5, 100.9, 82.4, 82.2, 75.8, 75.4, 33.8 (two peaks),
31.5, 22.6, 19.3, 14.2. Anal. Calcd for C22H16ClF3O3: C, 62.79;
H, 3.83%. Found: C, 62.62; H, 3.58%.
for C27H21ClO3: C, 75.61; H, 4.94%. Found: C, 75.43; H,
5.19%.
Methyl 4-(3-Methyl-5-oxo-7,7-diphenyl-2,5,7,8-tetra-
hydropyrano[4,3-b]pyran-2-yl)benzoate (7d): Yield 72%;
white solids; mp 174-175 °C (from ethyl acetate-hexane); IR
(KBr): ¯ = 3061, 2999, 2910, 1705, 1633, 1400, 1286, 1197
1
cm¹1; H NMR (600 MHz, CDCl3): ¤ 8.00-7.95 (m, 2H), 7.36
3,6-Bis(4-chlorophenyl)-7-methyl-3,4,5,6-tetrahydro-1H-
isochromen-1-one (3s): Yield 68%; white solids; mp 131-
132 °C (from ethyl acetate-hexane); IR (KBr): ¯ = 3068, 2931,
2910, 1608, 1489, 1398, 1296, 1157 cm¹1; 1H NMR (600 MHz,
CDCl3): ¤ 7.44-7.23 (m, 8H), 6.42 (s) and 6.36 (s) (total 1H),
5.71 (d, J = 16.2 Hz, 1H), 5.40 (dd, J = 10.8, 4.8 Hz) and 5.31
(dd, J = 11.9, 4.0 Hz) (total 1H), 2.79 (dd, J = 17.5, 12.0 Hz),
2.68-2.53 (m), 2.45 (dd, J = 17.5, 4.0 Hz) (total 2H), 1.63 (d,
J = 4.5 Hz, 3H); 13C NMR (151 MHz, CDCl3): ¤ 164.8, 164.5,
162.1, 161.7, 136.6, 136.5, 136.0 (two peaks), 135.4 (two
peaks), 134.4, 129.4, 129.3-129.1 (multiple peaks), 128.8 (two
peaks), 127.3 (two peaks), 125.4, 125.0, 113.9 (two peaks),
101.4, 100.9, 82.3, 82.2, 76.0, 75.6, 33.8, 19.3. Anal. Calcd for
C21H16Cl2O3: C, 65.13; H, 4.16%. Found: C, 65.46; H, 4.92%.
The compounds 7a-7d, 11a-11d, 13a, and 13b were
prepared in the same manner as described for 3a.
(dd, J = 8.3, 1.1 Hz, 2H), 7.34-7.16 (m, 10H), 6.26 (s, 1H),
5.71 (s, 1H), 3.95 (s, 3H), 3.27 (d, J = 17.5 Hz, 1H), 3.15 (d,
J = 17.5 Hz, 1H), 1.55 (s, 3H); 13C NMR (151 MHz, CDCl3):
¤ 166.5, 164.3, 161.8, 143.1, 142.5, 142.3, 130.9, 130.1, 128.4
(two peaks), 127.9-127.7 (multiple peaks), 125.7, 125.43,
124.4, 113.6, 102.1, 84.0, 82.5, 52.3, 37.2, 19.1. Anal. Calcd
for C29H24O5: C, 76.98; H, 5.35%. Found: C, 76.92; H, 5.29%.
tert-Butyl 7-(4-Chlorophenyl)-3-methyl-2-(4-nitrophen-
yl)-5-oxo-7,8-dihydro-2H-pyrano[3,2-c]pyridine-6(5H)-car-
boxylate (11a): Yield 71%; white solids; mp 87-88 °C (from
ethyl acetate-hexane); IR (KBr): ¯ = 3072, 2982, 2935, 1708,
1606, 1525, 1492, 1348, 1286, 1151, 1012 cm¹1; 1H NMR (600
MHz, CDCl3): ¤ 8.30-8.17 (m, 1H), 8.06-7.96 (m, 1H), 7.58-
7.48 (m, 1H), 7.33-7.27 (m, 1H), 7.22-7.17 (m, 1H), 7.17-7.11
(m, 2H), 7.02 (d, J = 8.3 Hz, 1H), 6.46 (d, J = 1.7 Hz, 1H),
5.63 (d, J = 20.0 Hz, 1H), 5.55 (dd, J = 24.5, 5.1 Hz, 1H),
3.25 (dd, J = 17.1, 6.2 Hz) and 3.05 (dd, J = 18.0, 6.7 Hz)
(total 1H), 2.56 (d, J = 17.0 Hz) and 2.48 (dd, J = 17.1, 2.1 Hz)
(total 1H), 1.61 (d, J = 12.6 Hz, 3H), 1.50 (d, J = 1.3 Hz,
9H); 13C NMR (151 MHz, CDCl3): ¤ 163.1, 162.6, 159.5,
144.4, 138.8, 133.5, 128.8 (two peaks), 128.5, 128.0, 126.9
(two peaks), 124.1 (three peaks), 123.8, 114.6, 114.0, 83.4
(two peaks), 81.3, 81.0, 54.5, 54.3, 33.5, 33.3, 28.2, 28.0
(two peaks), 19.2 (two peaks). Anal. Calcd for C26H25ClN2O6:
C, 62.84; H, 5.07; N, 5.64%. Found: C, 62.60; H, 4.92; N,
5.59%.
tert-Butyl 7-(4-Chlorophenyl)-2-(4-methoxyphenyl)-3-
methyl-5-oxo-7,8-dihydro-2H-pyrano[3,2-c]pyridine-6(5H)-
carboxylate (11b): Yield 69%; white solids; mp 83-84 °C
(from ethyl acetate-hexane); IR (KBr): ¯ = 3072, 2978, 2839,
1712, 1681, 1512, 1398, 1298, 1138 cm¹1; 1H NMR (600 MHz,
CDCl3): ¤ 7.32-7.24 (m, 2H), 7.21-7.13 (m, 2H), 7.04 (d,
J = 8.2 Hz, 1H), 6.95-6.86 (m, 2H), 6.72-6.67 (m, 1H), 6.39
(s, 1H), 5.58-5.47 (m, 2H), 3.81 (d, J = 6.6 Hz, 3H), 3.20 (dd,
J = 17.1, 6.2 Hz) and 3.03 (dd, J = 18.0, 6.7 Hz) (total 1H),
2.56-2.49 (m) and 2.46 (dd, J = 17.1, 2.1 Hz) (total 1H), 1.57
(d, J = 10.3 Hz, 3H), 1.51 (d, J = 3.1 Hz, 9H); 13C NMR (151
MHz, CDCl3): ¤ 159.3, 153.0 (two peaks), 130.4, 130.0, 129.4,
128.7 (two peaks), 128.5, 127.1 (two peaks), 125.5, 114.1,
113.9, 113.5, 112.8, 83.1 (two peaks), 82.6, 82.3, 55.3 (two
peaks), 54.4 (two peaks), 33.5, 33.2, 28.0, 19.3 (two peaks).
Anal. Calcd for C27H28ClNO5: C, 67.28; H, 5.86; N, 2.91%.
Found: C, 67.20; H, 5.53; N, 2.84%.
3-Methyl-2-(4-nitrophenyl)-7,7-diphenyl-7,8-dihydro-
pyrano[4,3-b]pyran-5(2H)-one (7a): Yield 73%; yellowish
solids; mp 104-105 °C (from ethyl acetate-hexane); IR (KBr):
¯ = 3059, 2912, 2856, 1708, 1633, 1523, 1398, 1346, 1228,
1
1166 cm¹1; H NMR (400 MHz, CDCl3): ¤ 8.17-8.10 (m, 2H),
7.43-7.13 (m, 12H), 6.32 (d, J = 0.6 Hz, 1H), 5.74 (s, 1H),
3.31 (d, J = 17.4 Hz, 1H), 3.16 (d, J = 17.4 Hz, 1H), 1.58
(d, J = 0.6 Hz, 3H); 13C NMR (101 MHz, CDCl3): ¤ 164.1,
161.6, 148.3, 144.3, 142.8, 142.2, 128.8-128.3 (multiple
peaks), 127.9 (two peaks), 125.4 (two peaks), 124.0 (two
peaks), 114.1, 102.4, 84.1, 81.6, 37.1, 19.0. Anal. Calcd for
C27H21NO5: C, 73.79; H, 4.82; N, 3.19%. Found: C, 73.71; H,
4.87; N, 3.14%.
2-(4-Methoxyphenyl)-3-methyl-7,7-diphenyl-7,8-dihydro-
pyrano[4,3-b]pyran-5(2H)-one (7b): Yield 68%; greenish
solids; mp 128-129 °C (from ethyl acetate-hexane); IR (KBr):
¯ = 3059, 2931, 2835, 1693, 1631, 1512, 1302, 1255, 1170
cm¹1; 1H NMR (600 MHz, CDCl3): ¤ 7.36 (dd, J = 8.3, 1.0 Hz,
2H), 7.34-7.13 (m, 10H), 6.85-6.81 (m, 2H), 6.23 (s, 1H), 5.64
(s, 1H), 3.84 (s, 3H), 3.23 (d, J = 17.6 Hz, 1H), 3.12 (d, J =
17.6 Hz, 1H), 1.56 (d, J = 7.8 Hz, 3H); 13C NMR (151 MHz,
CDCl3): ¤ 164.5, 161.9, 160.2, 143.4, 142.5, 130.1, 129.3,
128.4 (two peaks), 127.6 (two peaks), 125.8, 125.4, 125.1,
114.1, 113.2, 102.0, 83.9, 82.9, 55.3, 37.3, 19.2. Anal. Calcd
for C28H24O4: C, 79.22; H, 5.70%. Found: C, 79.23; H, 5.73%.
2-(4-Chlorophenyl)-3-methyl-7,7-diphenyl-7,8-dihydro-
pyrano[4,3-b]pyran-5(2H)-one (7c):
Yield 75%; white
solids; mp 70-71 °C (from ethyl acetate-hexane); IR (KBr):
¯ = 3061, 2924, 2854, 1708, 1633, 1448, 1398, 1230, 1166
cm¹1; 1H NMR (600 MHz, CDCl3): ¤ 7.36 (dd, J = 5.6, 3.7 Hz,
3H), 7.33-7.23 (m, 5H), 7.23-7.16 (m, 4H), 7.13 (d, J = 8.4
Hz, 2H), 6.27 (s, 1H), 5.64 (s, 1H), 3.25 (d, J = 17.5 Hz, 1H),
3.13 (d, J = 17.5 Hz, 1H), 1.57 (d, J = 9.8 Hz, 3H); 13C NMR
(151 MHz, CDCl3): ¤ 164.3, 161.7, 143.2, 142.3, 136.2, 135.2,
129.2, 128.4 (two peaks), 128.3, 127.7 (two peaks), 125.7,
125.4 (two peaks), 124.5, 113.7, 82.2, 37.2, 19.1. Anal. Calcd
tert-Butyl 7-(4-Chlorophenyl)-3-methyl-5-oxo-2-phenyl-
7,8-dihydro-2H-pyrano[3,2-c]pyridine-6(5H)-carboxylate
(11c): Yield 62%; white solids; mp 80-81 °C (from ethyl
acetate-hexane); IR (KBr): ¯ = 3063, 2980, 2931, 1712, 1629,
¹1
1492, 1396, 1296, 1138, 1089 cm
;
1H NMR (600 MHz,
CDCl3): ¤ 7.42-7.34 (m, 3H), 7.32-7.24 (m, 2H), 7.22-7.12
(m, 2H), 7.06-6.97 (m, 2H), 6.40 (s) and 6.26 (d, J = 15.9 Hz)
(total 1H), 5.59-5.53 (m) and 5.51 (d, J = 5.8 Hz) (total 2H),
3.21 (dd, J = 17.2, 6.3 Hz) and 3.05 (dd, J = 17.9, 6.7 Hz)